Process for making an aminosiloxane polymer nanoemulsion

ABSTRACT

Nanoemulsions are prepared by:
         a) solubilizing a silicone resin in an organic solvent system to yield a silicone resin solution concentration of 80% or less, wherein the organic solvent system comprises diethyleneglycol monobutyl ether and at least one additional solvent;   b) mixing the silicone resin solution from a) with an aminosiloxane polymer to obtain an aminosiloxane polymer: silicone resin mixture;   c) allowing the resin mixture to age for at least about 6 hours at ambient temperature;   d) adding the resin mixture to a vessel;   e) optionally adding with agitation an additional organic solvent to the resin mixture;   f) mixing until homogenous;   g) adding a protonating agent;   h) adding an aqueous carrier in an amount to produce a desired concentration of emulsion.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is the U.S. National Phase of PCT Appln. No.PCT/EP2015/067059 filed Jul. 24, 2015, which claims priority to EuropeanApplication No. 14178762 filed Jul. 28, 2014, the disclosures of whichare incorporated in their entirety by reference herein.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to method of making aminosiloxane polymernanoemulsions and nanoemulsion preparable by said method.

2. Description of the Related Art

Numerous attempts have been made to develop a treatment composition thatprovides protection of surfaces by repelling water and oil based soilsfrom the surface. Fluoropolymers, such as those used in Scotchguard®from 3M, have become well established as soil-repellant molecules.However, fluoropolymers are not preferred due to environmental, healthand safety concerns, such as the potential and possibility of persistentbioaccumulation and toxicity.

Amino-modified silicone microemulsions that contain an amino-modifiedsilicone and a high concentration of both ethylene glycol monoalkylether and nonionic surfactant, e.g., polyoxyalkylene branched decylether, are known and generally described as transparent in appearanceand having a small particle diameter. However, these compositions havethe challenge of delivering maximum hydrophobicity to a surface sincethey incorporate significant amounts of nonionic surfactant in order toobtain the desired stability and particle sizes.

Unfortunately, to date, attempts at non-fluorpolymer protection ofsurfaces continue to demonstrate disadvantages, including lowefficiency, difficulty in achieving the desired benefits at affordablecost, and in a preferred format, processing and formulation challenges,and product instability. A continued need exists for a non-fluoropolymertechnology that delivers depositable benefits to surfaces, such as waterand oily soil repellency, in a convenient and stable form and at a highefficiency.

Prior attempts at using non-fluoropolymer technologies have been lessthan successful due to a general failure to recognize the importance ofthe order of addition of materials during the preparation process aswell as the processing conditions themselves, in addition tooptimization of the solvent system, addition of adjunct ingredients thatcan enhance performance, and equally the removal of adjuncts that canhinder performance.

SUMMARY OF THE INVENTION

Applicants have surprisingly and unexpectedly discovered that aqueousaminopolysiloxane nanoemulsions free of the defects of the prior art canbe prepared by first dissolving a silicone resin in a solvent mixturecontaining dithyleneglycol monobutyl ether as one solvent, mixing thissolution with an amino-functional polysiloxane, ageing the resultantmixture, and further processing as described herein.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention thus provides a method of making a nanoemulsioncomprising the steps of:

-   -   a) solubilizing a silicone resin in an organic solvent system to        yield a silicone resin solution concentration of 80% or less,        wherein the organic solvent system comprises diethyleneglycol        monobutyl ether and at least one additional solvent selected        from monoalcohols, polyalcohols, ethers of monoalcohols, ethers        of polyalcohols, fatty esters, Guerbet alcohols, isoparaffins,        naphthols, glycol ethers or mixtures thereof, provided that if        the additional solvent is a glycol ether it is not        diethyleneglycol monobutyl ether;    -   b) mixing the silicone resin solution from a) with an        aminosiloxane polymer to obtain an aminosiloxane        polymer:silicone resin mixture having ratio of about 20:1;    -   c) allowing the aminosiloxane polymer:silicone resin mixture to        age for at least about 6 hours at ambient temperature;    -   d) adding the aminosiloxane polymer:silicone resin mixture to a        vessel;    -   e) optionally adding with agitation an additional organic        solvent to the aminosiloxane polymer:silicone resin mixture;    -   f) mixing until homogenous;    -   g) adding a protonating agent;    -   h) additionally adding an aqueous carrier in an amount to        produce the desired concentration of emulsion.

The present invention attempts to solve one more of the needs byproviding, in one aspect of the invention, a method of making anaminosilicone nanoemulsion which can be incorporated into a surfacetreatment composition.

Applicants have found that by optimizing the order of addition of theraw materials during emulsion making and finished product formulationusing said emulsion, the overall stability of the emulsion and finishedproduct can be greatly enhanced. Furthermore, the deposition efficiencyand overall soil repellency benefit can be maximized, whilst minimizingthe potential for negative results often seen with silicone-containingcompositions, such as staining or spotting of fabrics, laundry machineresidues, and product discoloration.

As used herein, the articles including “the,” “a” and “an” when used ina claim or in the specification, are understood to mean one or more ofwhat is claimed or described.

As used herein, the terms “include,” “includes” and “including” aremeant to be non-limiting.

As used herein, the terms “substantially free of” or “substantially freefrom” means that the indicated material is at the very minimum notdeliberately added to the composition to form part of it, or,preferably, is not present at analytically detectable levels. It ismeant to include compositions whereby the indicated material is presentonly as an impurity in one of the other materials deliberately included.Preferably, substantially free from surfactant means that the emulsioncomprises at most 1 percent by weight of surfactant, more preferably atmost 0.1 percent by weight of surfactant.

As used herein, the term nanoemulsion refers to thermodynamically stableoil in water emulsions that have extremely small droplet sizes (below750 nm, or typically below 250 nm). These materials have specialproperties, including optical translucency, very large dispersed phasesurface-to-volume ratios and long term kinetic stability. Due tosimilarity in appearance, translucent nanoemulsions are sometimesconfused with microemulsions, which belong to another class of stable(thermodynamically) and optically clear colloidal systems.Microemulsions are spontaneously formed by “solubilizing” oil moleculeswith a mixture of surfactants, co-surfactants and co-solvents. Therequired surfactant concentration in a microemulsion is typicallyseveral times higher than that in a nanoemulsion and significantlyexceeds the concentration of the dispersed phase (generally, oil).Because of many undesirable side-effects caused by surfactants, this isdisadvantageous or prohibitive for many applications. In addition, thestability of microemulsions is easily compromised by dilution, heating,or changing pH levels. By contrast nanoemulsions in accordance with thepresent invention are formed by judiciously selecting solvent systemsthat provide adequate dissolution of the siloxanes and also exhibit somelevel of miscibility with water, thus a stable aqueous emulsion can beachieved without the use of surfactants. Without wishing to be bound bytheory, applicants believe that choosing a solvent or solvent systemwhereby the solvents exhibit dual polarity, these solvents of choice canbehave similarly to surfactants in solution without introducing thewetting effect that surfactants typically bring. Thus, it is possible todeliver an oil-in-water emulsion, without having surfactant present,that is capable of providing maximum hydrophobicity to a target surface.

All cited patents and other documents are, in relevant part,incorporated by reference as if fully restated herein. The citation ofany patent or other document is not an admission that the cited patentor other document is prior art with respect to the present invention.

In this description, all concentrations and ratios are on a weight basisof the total nanoemulsion composition, all pressures are equal to 0.10MPa (absolute) and all temperatures are equal to 20° C., unlessotherwise specified.

Known amino silicone microemulsions and methods for preparing aminosilicone microemulsions employ high levels of solvent and nonionicsurfactant (e.g., 12% ethylene glycol monohexyl ether per 100% of aminosilicone and 40% polyoxyalkylene branched decyl ether per 100% of aminosilicone), and/or require high energy in the form of heat or highshearing forces in order to obtain the desired nanoparticle size.Without being bound by theory, it is believed that the presence of highlevels of solvent and surfactant in the emulsion hinders the depositionof the amino silicone on the surface that is to be treated; aminosilicone droplets in high-solvent and high-surfactant emulsions tend tostay in the emulsion, rather than deposit on the surface. This resultsin a poor delivery of any benefit, such as increased water repellency oroil repellency, to the surface. Such benefits may be measured as anincreased time to wick on treated fabrics, a reduced dry-time fortreated fabrics and/or an increased contact angle on a hard surface.

In contrast to conventional amino silicone microemulsions, the aminosilicone nanoemulsions of the present invention comprise reduced levelsof solvent and no intentionally added surfactant and may be obtainedwithout the input of high energy to process the emulsion. Yet, the aminosilicone nanoemulsions disclosed herein provide highly efficientdeposition on a target surface. Benefits derived from this depositionmay generally apply in the area of repellency of water and/orwater-based compositions and/or oil and/or oil-based compositions, suchas water-based stains and oily soils. Without being bound by theory, itis believed that the amino silicone nanoemulsions disclosed hereincomprise self-assembled, spherical, positively charged amino siliconenano-particles (which contain reduced levels of solvent and surfactant).These self-assembled, spherical, positively charged nano-particlesexhibit efficient deposition and controlled spreading, that is believedto form a structured film on a surface that provides the repellencybenefit as determined by the time to wick method specified below.

The average particle sizes of the disclosed nanoemulsions range from 20nm to 750 nm, or 20 nm to 500 nm, or 50 nm to 350 nm, or 80nm to 200 nm,or 90nm to 150 nm (as measured by Malvern Zetasizer Nano Seriesinstrument.). The disclosed nanoemulsions are generally transparent orslightly milky in appearance.

Typically, the aminosiloxane polymer nanoemulsion of the presentinvention comprises a silicone resin.

An example of a silicone resin is a mixture ofpolyorganosiloxane-silicone resins, where each of the one or moresilicone resins of the polyorganosiloxane-silicone resin mixturecontains at least about 80 mol % of units selected from the groupconsisting of units of the general formulas 3, 4, 5, 6:

R₃SiO_(1/2)   (3),

R₂SiO_(2/2)   (4),

RSiO_(3/2)   (5),

SiO_(4/2)   (6)

in which R is selected from H, −OR¹⁰, or —OH residues or monovalenthydrocarbon residues with 1 to 40 carbon atoms, optionally substitutedwith halogens, where at least 20 mol % of the units are selected fromthe group consisting of units of the general formulas 5 and 6, and amaximum of 10 wt % of the R residues are —OR¹⁰ and —OH residues.

The silicone resins are preferably MQ silicon resins (MQ) comprising atleast 80 mol % of units, preferably at least 95 mol % and particularlyat least 97 mol % of units of the general formulae 3 and 6. The averageratio of units of the general formulae 3 to 6 is preferably at least0.25, more preferably at least 0.5, and preferably at most 4, morepreferably at most 1.5.

The silicon resins may also preferably be DT silicone resins (DT)comprising at least 80 mol % of units, preferably at least 95 mol % andparticularly at least 97 mol % of units of the general formulae 4 and 5.The average ratio of units of the general formulae 4 to 5 is preferablyat least 0.01, more preferably at least 0.2, and preferably at most 3.5,more preferably at most 0.5.

Preferred halogen substituents of the hydrocarbon residues R arefluorine and chlorine. Preferred monovalent hydrocarbyl radicals R aremethyl, ethyl, phenyl.

Preferred monovalent hydrocarbyl radicals R¹⁰ are methyl, ethyl, propyland butyl.

Suitable aminosiloxane polymers are represented by liquidaminoalkyl-containing polyorganosiloxanes (P) comprising at least 80 mol% of units selected from units of the general formulae 7, 8, 9 and 10

R¹ ₂SiO_(2/2)   (7),

R¹ _(a)R² _(b)SiO_((4-a-b)/2)   (8),

R³ ₃SiO_((1/2l ))   (9),

R³ ₂R⁴SiO_((1/2))   (10),

where

-   a has the value 0 or 1,-   b has the value 1 or 2,-   a+b has a value of 2,-   R¹ represents monovalent hydrocarbyl radicals having 1-40 carbon    atoms and optionally substituted with halogens,-   R² represents either-   a) aminoalkyl radicals of the general formula 11

—R⁵—NR⁶R⁷   (11)

where

-   R⁵ represents divalent hydrocarbyl radicals having 1-40 carbon    atoms,-   R⁶ represents monovalent hydrocarbyl radicals having 1-40 carbon    atoms, H, hydroxymethyl or alkanoyl radicals, and-   R⁷ represents a radical of the general formula 12

—(R⁸—NR⁶)_(x)R⁶   (12)

where

-   x has the value 0 or an integer value from 1 to 40, and-   R⁸ represents a divalent radical of the general formula 13

—(CR⁹ ₂—)_(y)   (13)

where

-   Y has an integer value from 1 to 6, and-   R⁹ represents H or hydrocarbyl radicals having 1-40 carbon atoms, or-   b) in the general formula 11 R⁶ and R⁷ combine with the nitrogen    atom to form a cyclic organic radical having 3 to 8 —CH₂— units,    although nonadjacent —CH₂— units may be replaced by units selected    from —C(═O)—, —NH—, —O— and —S—,-   R³ represents hydrocarbyl radicals having 1-40 carbon atoms and    optionally substituted with halogens,-   R⁴ represents —OR or —OH radicals, and wherein, in the    polyorganosiloxanes (P), the average ratio of the sum of units of    the general formulae 7 and 8 to the sum of units of the general    formulae 9 and 10 is in the range from 0.5 to 500, the average ratio    of units 9 to 10 being in the range from 1.86 to 100, and the    polyorganosiloxanes (P) have an average amine number of at least    0.01 mequiv/g.

The monohydric hydrocarbyl radicals R, R¹, R³, R⁶, R⁹ and R¹⁰ may behalogen substituted, linear, cyclic, branched, aromatic, saturated orunsaturated. Preferably, the monovalent hydrocarbyl radicals R, R¹, R³,R⁶, R⁹ and R¹⁰ each have 1 to 6 carbon atoms, and particular preferenceis given to alkyl radicals and phenyl radicals. Preferred halogensubstituents are fluorine and chlorine. Particularly preferredmonovalent hydrocarbyl radicals R, R¹, R³, R⁶, R⁹ and R¹⁰ are methyl,ethyl, phenyl.

The divalent hydrocarbyl radicals R⁵ may be halogen substituted, linear,cyclic, branched, aromatic, saturated or unsaturated. Preferably, the R⁵radicals have 1 to 10 carbon atoms, and particular preference is givento alkylene radicals having 1 to 6 carbon atoms, in particularpropylene. Preferred halogen substituents are fluorine and chlorine.

Preferred R⁶ radicals are alkyl and alkanoyl radicals. Preferred halogensubstituents are fluorine and chlorine. Preferred alkanoyl radicals are—C(═O)R¹¹, where R¹¹ has the meanings and preferred meanings of R¹.Particularly preferred substituents R⁶ are methyl, ethyl, cyclohexyl,acetyl and H. It is particularly preferable for the R⁶ and R⁷ radicalsto be H.

Preferred cyclic organic radicals formed from R⁶ and R⁷ in the generalformula 11 together with the attached nitrogen atom are the five and sixmembered rings, in particular the residues of pyrrolidine,pyrrolidin-2-one, pyrrolidine-2,4-dione, pyrrolidin-3-one,pyrazol-3-one, oxazolidine, oxazolidin-2-one, thiazolidine,thiazolidin-2-one, piperidine, piperazine, piperazine-2,5-dione andmorpholine.

Particularly preferred R² radicals are —CH₂NR⁶R⁷, —(CH₂)₃NR⁶R⁷ and—(CH₂)₃N(R⁶)(CH₂)₂N(R⁶)₂. Examples of particularly preferred R² radicalsare aminoethylaminopropyl and cyclohexylaminopropyl.

Preference is also given to mixtures (M) wherein at least 1 mol %, morepreferably at least 5 mol %, most preferably at least 20 mol %, and atmost 90 mol %, more preferably at most 70 mol % and particularly at most60 mol % of the R⁶ and R⁷ radicals are acetyl radicals and the remainingR⁶ and R⁷ radicals are H.

Preferably, b is 1. Preferably, a+b has an average value from 1.9 to2.2.

Preferably, x has the value 0 or a value from 1 to 18, more preferably 1to 6.

Preferably, y has the values of 1, 2 or 3.

Preferably, the polydiorganosiloxanes (P) comprise at least 3 andparticularly at least 10 units of the general formulae 7 and 8.

Preferably, the liquid aminoalkyl-containing polyorganosiloxanes (P)comprise at least 95 mol %, more preferably at least 98 mol % andparticularly at least 99.5 mol % of units selected from units of thegeneral formulae 7, 8, 9 and 10.

Further units of the polyorganosiloxanes (P) can be selected for examplefrom units selected from units of the general formulae 3, 4, 5, 6.

The ratio of a to b is chosen such that the polyorganosiloxanes (P)preferably have an amine number of at least 0.1, in particular at least0.3 mequiv/g of polyorganosiloxane (P). The amine number of thepolyorganosiloxanes (P) is preferably at most 7, more preferably at most4.0 and particularly at most 3.0 mequiv/g of polyorganosiloxane (P).

The amine number designates the number of ml of 1N HCl which arerequired for neutralizing 1 g of polyorganosiloxane (P).

The viscosity of the polyorganosiloxanes (P) is preferably at least 1and particularly at least 10 mPa·s and preferably at most 100,000 andparticularly at most 10,000 mPa·s at 25° C.

The ratio of the units of the general formulae 7 and 8 to the sum totalof 9 and 10 is preferably at least 10, more preferably at least 50, andpreferably at most 250, particularly at most 150.

The ratio of units 9 to 10 is preferably at least 1.9 and particularlyat least 2.0 and preferably at most 70 and particularly at most 50.

The polyorganosiloxanes (P) are obtainable via known chemical processessuch as, for example, hydrolysis or equilibration.

The aminosiloxane polymer nanoemulsion of the present inventioncomprises from 0.1% to 50% of one or more solvents, relative to theweight of the aminosiloxane polymer. In certain aspects, theaminosiloxane polymer nanoemulsion comprises from 5% to 30% of one ormore solvents, relative to the weight of the aminosiloxane polymer. Insome aspects, the aminosiloxane polymer nanoemulsion comprises from 10%to 25% of one or more solvents, relative to the weight of theaminosiloxane polymer. In other aspects, the aminosiloxane polymernanoemulsion comprises from 15% to 23% or from 18% to 21% of one or moresolvents, relative to the weight of the aminosiloxane polymer.

In one aspect of the invention the solvent system contains at least twosolvents wherein one is diethyleneglycol monobutyl ether, such as thatsold under the trade name Butyl Carbitol™ from Dow Chemical (Midland,Mich.), and additional solvent(s) are selected from monoalcohols,polyalcohols, ethers of monoalcohols, ethers of polyalcohols, fattyesters, Guerbet alcohols, isoparaffins, naphthols, glycol ethers ormixtures thereof, provided that if the additional solvent is a glycolether it is not diethyleneglycol monobutyl ether.

In some aspects, the solvent is selected from a mono-, di-, ortri-ethylene glycol monoalkyl ether that comprises an alkyl group having1-12 carbon atoms, or a mixture thereof. Suitable alkyl groups includemethyl, ethyl, propyl, butyl groups, hexyl groups, heptyl groups, octylgroups, nonyl groups, decyl groups, undecyl groups, phenyl, and dodecylgroups, as well as acetate groups of each.

Suitable examples of monoethylene glycol monoalkyl ethers includeethyleneglycol methyl ether, ethyleneglycol ethyl ether, ethyleneglycolpropyl ether, ethyleneglycol butyl ether, ethyleneglycol butyl etheracetate, ethyleneglycol phenyl ether, ethyleneglycol hexyl ether, andcombinations thereof.

Suitable examples of diethylene glycol monoalkyl ethers includediethyleneglycol methyl ether, diethyleneglycol ethyl ether,diethyleneglycol propyl ether, diethyleneglycol butyl ether,diethyleneglycol phenyl ether, diethyleneglycol hexyl ether, andcombinations thereof.

In some aspects, the solvent is selected from a mono-, di-, ortri-propylene glycol monoalkyl ether that comprises an alkyl grouphaving 1-12 carbon atoms, or a mixture thereof. Suitable alkyl groupsinclude methyl, ethyl, propyl, and butyl groups, hexyl groups, heptylgroups, octyl groups, nonyl groups, decyl groups, undecyl groups,dodecyl groups, and phenyl groups as well as acetate groups of each.

Suitable examples of monopropylene glycol monoalkyl ethers includepropyleneglycol methyl ether, propyleneglycol methyl ether acetate,propyleneglycol methyl ether diacetate, propyleneglycol propyl ether,propyleneglycol butyl ether, propyleneglycol phenyl ether, andcombinations thereof.

Suitable examples of dipropylene glycol monoalkyl ethers includedipropyleneglycol methyl ether, dipropyleneglycol methyl ether acetate,dipropyleneglycol propyl ether, dipropyleneglycol butyl ether, andcombinations thereof.

Suitable examples of tripropylene glycol monoalkyl ethers includetripropyleneglycol methyl ether, tripropyleneglycol propyl ether,tripropyleneglycol butyl ether, and combinations thereof.

In some aspects the solvent is selected from fatty esters such asisopropyl esters of long chain fatty acids having 8 to 21 carbon atoms.Suitable examples of fatty esters include isopropyl laurate, isopropylmyristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate,isopropyl linoleate, and combinations thereof.

In some aspects, the solvent comprises a linear or branched mono- orpolyhydric alcohol, or a Guerbet alcohol, such as 2-ethylhexanol,2-butyloctanol, or 2-hexyldecanol, or mixtures thereof.

In some aspects the solvent comprises a naphthol or isoparaffin havingfrom about 8 to about 16 carbon atoms, such as isoparaffins sold underthe trade name Isopar E™, Isopar L^(™), Isopar G™, or Isopar M™(available from ExxonMobile Chemicals, Houston, Tex.).

The protonating agent is generally a monoprotic or multiprotic,water-soluble or water-insoluble, organic or inorganic acid. Suitableprotonating agents include, for example, formic acid, acetic acid,propionic acid, malonic acid, citric acid, hydrochloric acid, sulfuricacid, phosphoric acid, nitric acid, or mixtures thereof. In someaspects, the protonating agent is selected from formic acid, aceticacid, or a mixture thereof. In some aspects, the protonating agent isacetic acid. Generally, the acid is added in the form of an acidicaqueous solution. The protonating agent is added in an amount necessaryto achieve a nanoemulsion pH of from 3.5 to 7.0. In certain aspects, theaminosiloxane polymer nanoemulsions comprise the protonating agent in anamount necessary to achieve a pH of from 3.5 to 6.5 or 4.0 to 6.0. Inother aspects, the aminosiloxane polymer nanoemulsions comprise theprotonating agent in an amount necessary to achieve a pH of mostpreferably from 3.5 to 5.0.

The aminosilicone nanoemulsions of the present invention can be dilutedto produce any desired concentration of nanoemulsion by the addition ofwater.

The aminosiloxane polymer nanoemulsions may additionally include furthersubstances, such as preservatives, scents, corrosion inhibitors, UVabsorbers, structurants, opacifiers, optical brighteners, and dyes.Examples of preservatives are alcohols, formaldehyde, parabens, benzylalcohol, propionic acid and salts thereof and also isothiazolinones. Thenanoemulsions may further include yet other additives, such asnon-silicon-containing oils and waxes. Examples thereof are rapeseedoil, olive oil, mineral oil, paraffin oil or non-silicon-containingwaxes, for example carnauba wax and candelilla wax incipiently oxidizedsynthetic paraffins, polyethylene waxes, polyvinyl ether waxes andmetal-soap-containing waxes. In some aspects, the aminosiloxane polymernanoemulsions further comprise carnauba wax, paraffin wax, polyethylenewax, or a mixture thereof. The nanoemulsions may comprise up to about 5%by weight of the nanoemulsion or from 0.05% to 2.5% by weight of thenanoemulsion of such further substances.

The method for preparing the amino silicone nanoemulsions of the presentinvention includes the steps of: solubilizing the silicone resin in anorganic solvent or mixture of organic solvents to yield a resin solutionconcentration of 80% or less, preferably of 70% or less, more preferablyof 60% or less, or most preferably of 55% or less, followed by mixingthe resin solution with an amino siloxane polymer to obtain an aminosiloxane polymer:resin ratio of about 20:1, preferably about 10:1, morepreferably about 7:1, most preferably about 5.8:1, and allowing themixture to age for at least about 6 hours at room temperature; theemulsion is then prepared by adding the amino siloxane polymer:resinmixture to a vessel containing a small amount of water with agitation,optionally followed by addition of a second organic solvent to aid inthe dispersion of the amino siloxane polymer:resin mixture in aqueouscarrier. Once the solvent, silicone and carrier mixture has becomehomogenous, then the protonating agent is added, followed by additionalamounts of carrier to produce a nanoemulsion at the desiredconcentration. Optional adjunct materials are then added to the mixtureand agitated until thoroughly mixed.

The aminosiloxane polymer nanoemulsions of the present invention may beincorporated into treatment compositions or cleaning compositions, suchas, but not limited to, a fabric care composition, a hard surface carecomposition, or a home care composition.

Examples of treatment compositions include, but are not limited to,laundry spray treatment products, laundry pre-treatment products, fabricenhancer products, hard surface treatment compositions (hard surfacesinclude exterior surfaces, such as vinyl siding, windows, and decks),carpet treatment compositions, and household treatment compositions.Examples of fabric care compositions suitable for the present disclosureinclude, but are not limited to, laundry spray treatment products,laundry pre-treatment products, laundry soak products, and rinseadditives. Examples of suitable home care compositions include, but arenot limited to, rug or carpet treatment compositions, hard surfacetreatment compositions, floor treatment compositions, and windowtreatment compositions.

In some aspects, the treatment composition may be provided incombination with a nonwoven substrate, as a treatment implement.

In certain aspects, the compositions provide water and/or oil repellencyto the treated surfaces, thereby reducing the propensity of the treatedsurface to become stained by deposited water- or oil-based soils.

By “surfaces” it is meant any surface. These surfaces may include porousor non-porous, absorptive or non-absorptive substrates. Surfaces mayinclude, but are not limited to, celluloses, paper, natural and/orsynthetic textiles fibers and fabrics, imitation leather and leather.Selected aspects of the present invention are applied to natural and/orsynthetic textile fibers and fabrics.

By “treating a surface” it is meant the application of the compositiononto the surface. The application may be performed directly, such asspraying or wiping the composition onto a hard surface. The compositionmay or may not be rinsed off, depending on the desired benefit.

Test Methods Time to Wick (T2W) Measurement Method: The fabric Time toWick property is a measure of the water repellency of a fabric, wherelonger times indicate greater repellency. Water repellency is measuredwhen a drop of water is applied to the fabric, such as white 6.1 oz(165-200 gsm) Gildan Ultra 100% Cotton t-shirts (size large, item number2000, Gildan USA, Charleston, S.C.). The Gildan t-shirts are prepared byde-sizing for 2 cycles of laundering with clean rinses using the AATCC2003 standard reference liquid detergent without optical brighteners(AATCC—American Association of Textile Chemists and Colorists, ResearchTriangle Park, N.C., USA) in a standard top-loader, North American stylewashing machine, such as a Kenmore 600 Model 110.28622701. Fortreatment, 12 t-shirts are added to the drum of a standard washingmachine, set on Heavy Duty wash cycle, water level equal to 17 gallons(Super load size), warm water, selected with single rinse option. Wateris regulated to standardize the wash temperature to 90° F., Rinse to 60°F., and water hardness to 6 grain per gallon. Detergent is added to thewash water, such as Tide liquid Detergent (50.0g dose), Clean Breezescent. With the fabrics in the washer, the rinse water is allowed tofill the tub. Prior to agitation, the fabric treatment composition ofthe present invention (40 grams) is equally dispersed and added to therinse water, followed by completion of the rinse cycle. The garments arethen placed in a standard dryer, such as a Kenmore standard 80 series,cotton cycle (high heat), for 30 minutes or until dry. The fabrics arethen removed from the dryer and placed in a cool, well ventilated roomwith controlled humidity set at 50% RH, and temperature regulated to 70°F., for a period of 24-48 hours.

The section of the fabric that will be measured for Time to Wick issubjected to UV light, such as standard overhead lab lighting, for 24-48hours prior to measurement. Treated test fabric is compared for Time toWick value versus an untreated control fabric that has been prepared ina similar manner as the test fabric without the addition of the fabrictreatment composition.

The Time to Wick value is measured as follows: On a flat, level hardsurface (e.g. benchtop) a fresh square of a paper towel at least 10cm×10cm in size, is placed inside the prepared t-shirt so that 1 layerof fabric is being measured. A 300 μL drop of DI water is then dispensedonto the fabric surface from a calibrated pipette. The process ofabsorption of the liquid drop is visually monitored and recordedcounting the time elapsed in seconds. Eight drops are administered pert-shirt, with each drop placed at a different location separate from alladjacent drops.

For each drop, the time differential between when the drop is appliedand when absorbed is calculated and recorded in seconds. The time atdrop absorption is defined as being the earliest time point at which noportion of the drop is observed remaining above the surface of thefabric. If the drop remains after 10 minutes, observation isdiscontinued. Such drops are recorded as having a time differential of600 seconds. The Time to Wick value for a given liquid on fabric is theaverage of the time differentials recorded for 8 drops of that liquid.In order to determine the effect of a treatment, comparisons are madebetween the average Time to Wick value obtained from the treated fabric,versus the average obtained from its untreated control fabric using thesame liquid, where longer times indicate greater repellency.

Particle Size Measurement Test Method by Using Malvern Zetasizer Nano ZS

The organosilicone nanoemulsions finished product containing thenanoemulsions are measured either neat or diluted with DI water to aspecific concentration (1:10, 1:500 or 1:1000) with filtered DI water(using Gelman acrodisc LC PVDF 0.45 μm) prior to making particle sizemeasurements. The particle size measurement is performed immediatelyafter the sample completely disperses in water. The data is reported asthe average of 3 readings.

Sample Preparation

The dilution used will be dependent upon the type of sample: siliconeemulsions are diluted at a concentration of 1:500 and 1:1000 and finishproducts are measured as neat and diluted to a concentration of 1:10 inDI water.

-   -   Before diluting the sample, gently invert it several times to        mix it well.    -   Rinse the 10 ml vial with filtered DI water to remove any dust        then pipette a specific amount of filtered DI water and sample        to the vial to make up the correct concentration (1:10, 1:500 or        1:1000). Invert the vial several times to make sure the sample        completely disperses in water.    -   Add 1 ml of diluted sample or neat sample to a clean cuvette        ensuring that there are no air bubbles present in the sample.

Instrument Set up Conditions:

The particle size measurements are made via Malvern Zetasizer NanoSeries ZS, with model #ZEN3600 with the fixed parameter settings forboth Silicone emulsion and finish product:

Material: Silicone Refractive Index (RI) 1.400 Absorption 0.001Dispersion: Water Temp. 25° C. Viscosity 0.8872 cP RI 1.33

General Option:Using dispersant viscosity as sample viscosity

Temperature: 25° C. Aging time: 0 second Cell Type: DTS0012 - Disposablesizing cuvette Measurement: Meas. Angle 173° Backscatter (NIBS default)Meas. Duration Manual Number of runs 3 Run duration 60 s Number of Meas.3 Delay between meas. 0 s Positioning method Seek for optimum positionAutomatic attenuation selection Yes Data Processing: Analysis modelGeneral purpose (normal resolution)

Time to Dry Test Method:

Test Method for Determining the Range of Nanoparticle Typical Diametersand the Presence/Absence of Nanoparticle Aggregates, Using aCryo-Transmission Electron Microscope (Cryo-TEM).

Samples of the liquid composition to be tested are prepared formicroscopic analysis in order to observe nanoparticles that may besuspended in the composition. Sample preparation involves pipettingapproximately 5 μl of the liquid composition onto a holey carbon grid(such as Lacey Formvar Carbon on 300 mesh copper grid, P/N 01883-F,available from Ted Pella Inc., Redding, Calif., U.S.A., or similar). Theexcess liquid is blotted away from the edge of the grid with a filterpaper (such as Whatman brand #4, 70 mm diameter, manufactured by GEHealthcare/General Electric Company, Fairfield, Conn., U.S.A., orsimilar). The grid-mounted sample is plunged rapidly into liquid ethaneusing a freezing apparatus capable of producing a flash-frozen vitreousthin film of sample lacking crystalline ice (such as a ControlledEnvironment Vitrification System (CEVS device), or similar apparatus).The apparatus configuration and use of a CEVS device is described in theJournal of Electron Microscopy Technique volume 10 (1988) pages 87-111.Liquid ethane may be prepared by filling an insulated container withliquid nitrogen and placing a second smaller vessel into the liquidnitrogen. Gaseous ethane blown through a syringe needle into the secondvessel will condense into liquid ethane. Tweezers pre-cooled in liquidnitrogen are used to rapidly handle the frozen grids while taking greatcare to maintain the vitreous non-crystalline state of the sample andminimize the formation of frost on the sample. After being flash frozenthe grid-mounted samples are stored under liquid nitrogen until beingloaded into the cryo-TEM via a cryo transfer holder (such as Gatan model626 Cryo-Holder available from Gatan Inc., Warrendale, Pa., U.S.A.,attached to a TEM instrument such as the model Tecnai G² 20 availablefrom FEI Company, Hillsboro, Oreg., U.S.A., or similar). The cryo-TEM isequipped with a camera such as the Gatan Model 994 UltraScan 1000XP(available from Gatan Inc., Warrendale, Pa., U.S.A.). The grid-mountedfrozen samples are imaged in the cryo-TEM using low beam dosages (suchas 200 KV in Low Dose Mode) in order to minimize sample damage. Suitablemagnifications are selected in order to observe the size ofnanoparticles which may be present. This may include magnifications inthe range of 5,000×-25,000×. During imaging the sample is kept as coldas possible, typically at or near the temperature of liquid nitrogen(approximately minus 175° C.). Images of the samples are carefullyexamined to detect the presence of artefacts. A grid-mounted sample isdiscarded if any crystalline ice. Images are inspected for beam damageartefacts and are rejected if damage is observed. For each grid-mountedsample, representative images are captured of approximately 40 fields ofview which are representative of the sample. These images are used todetermine the range of nanoparticle typical diameters, and to determinethe presence or absence of nanoparticle aggregates. In each image, thediameters are measured from nanoparticles which are typical of thatimage. The range of typical diameter values reported for the compositionis the range of the diameters measured across all images captured fromthat composition. In each image, the spacing between nanoparticles isobserved. A nanoparticle aggregate is defined as a cluster whichcontains at least 10 nanoparticles clumped together, rather than beingindividually dispersed. Nanoparticle aggregates are reported as presentif at least one nanoparticle aggregate is observed in at least one imagecaptured from that composition.

EXAMPLES SOLVENT EXAMPLES

The following list of solvent options is for illustrative purposes ofmaking the silicone resin solution of example prep 2 below and isconsidered to be non-limiting:

TABLE I Example Solvents A B C Guerbet 2-Ethylhexanol¹ 2-Butyloctanol²2-Hexyldecanol³ Alcohols D E F Glycol Propyleneglycol DipropyleneglycolTripropyleneglycol Ethers n-Butyl ether⁴ n-Butyl ether⁵ n-Butyl ether⁶ GH I Fatty Isopropyl Isopropyl Isopropyl Esters Laurate⁷ Myristate⁸Palmitate⁹

1. Preparation of Resin Solution

In a 400 mL beaker add specified amount of MQ resin powder({[Me₃SiO_(1/2)]_(0.373)[SiO₂]_(0.627)}₄₀, Mn=2700 g/mol, resin contains0.2% OH and 3.1% OEt [corresponds to OR¹⁰]) according to Table II below;slowly add solvent(s) and begin mixing using an Ika RWA-20 mixer with a4-blade agitator (2 inch diameter tip-to-tip) having 45° pitch on eachblade using appropriate level of agitation. Continue with gentle mixinguntil all resin powder is completely dissolved; allow solution to settleat least 24 hours to allow for complete de-aeration.

TABLE II Example Resin solution compositions Resin Solution ExamplesComponent J K L M N O P Q R S T Resin 55.7 55.7 55.7 55.7 55.7 55.7 55.755.7 55.7 55.7 55.7 Powder¹⁰ Total 44.3 44.3 44.3 44.3 44.3 44.3 44.344.3 44.3 44.3 44.3 Solvent wt. (g) Butyl 0 2.0 4.0 6.0 8.0 10.0 12.014.0 16.0 18.0 19.0 Carbitol¹¹ Solvent A-I 44.3 42.3 40.3 38.3 36.3 34.332.3 30.3 28.3 26.3 25.3

2. Preparation of Resin-Aminosilicone Oil Mixture

To a 6 oz. glass container add 76.3 g of aminosilicone fluid and 23.7 gof resin solution according to Table III below. The amine oil U has aviscosity about 1000 mm²/s at 25° C. [corresponds to units of formulas7+8+9+10=230], functional radicals —(CH₂)₃NH(CH₂)NH₂ [corresponds toR²], amine number of 0.5 mmol/g, 92% SiMe₃ end groups, and 8% SiMe₂OHend groups [corresponds to units of formulas 9/10=11.5].

The amine oil V has a viscosity about 1000 mm²/s at 25° C. [correspondsto units of formulas 7+8+9+10=230], functional radicals—(CH₂)₃NH(CH₂)NH₂ [corresponds to R²], amine number of 0.5 mmol/g, 85%SiMe₃ end groups, and 15% SiMe₂OH end groups [corresponds to units offormulas 9/10=5.7].

The amine oil W has a viscosity about 1000 mm²/s at 25° C. [correspondsto units of formulas 7+8+9+10=230], functional radicals—(CH₂)₃NH(CH₂)NH₂ [corresponds to R²], amine number of 0.5 mmol/g, 80%SiMe₃ end groups, and 20% SiMe₂OH end groups [corresponds to units offormulas 9/10=4.0].

Mix fluids until completely homogenous using an Ika® RWA-20 mixer with a4-blade agitator having 45° pitch on each blade using appropriate levelof agitation. Place lid on container and allow oil mixture to age atroom temperature for at least 72 hours.

TABLE III Example Resin-Aminosilicone Oil mixture solutionsResin-AminoSilicone Oil Mixture Examples Example U V W Aminosilicone 8%—OH 15% —OH 20% —OH Terminal group termination termination terminationAminosilicone 76.3 76.3 76.3 amt. (g) Resin solution, 23.7 23.7 23.7 Ex.J-T (g)

3. Preparation of Aminosilicone-Resin Emulsion

In a 250 mL beaker add 78.0 g of oil mixture from examples U-W above,followed by additional solvent according to Table IV below. Begin mixingsolution using an Ika® RWA-20 mixer with a 4-blade agitator having 45°pitch on each blade using appropriate level of agitation. Continuemixing; once solvent has completely incorporated, add specifiedprotonation agent to the mixture; add remaining water slowly and in 3separate but equal increments, allowing each addition to fullyincorporate prior to adding the next. Continue agitation to ensure themixture is completely emulsified.

TABLE IV Example Aminosilicone-Resin Emulsions Silicone-Resin EmulsionExamples Component (g) AA BB CC DD EE FF Oil Mix. Example 39.0 39.0 39.039.0 39.0 39.0 U-W Solvent from — 1.5 1.2 0.8 9.75 19.5 examples A-I¹⁻⁹Butyl Carbitol¹¹ 19.5 18.0 18.3 18.7 9.75 0.0 Resin Composition T J, T TT T J-T from Table II Protonating 0.9 0.9 0.9 0.9 0.9 0.9 Agent¹² Water(13.5 g × 3) 40.6 40.6 40.6 40.6 40.6 40.6 Total Amount (g) 100.0 100.0100.0 100.0 100.0 100.0

4. Finished Product Formulation Examples

In a 400 mL beaker, add specified amount of emulsion from examplesAA-FF, followed by perfume; begin mixing solution using an Ika® RWA-20mixer with a 4-blade agitator having 45° pitch on each blade usingappropriate level of agitation. Add solvent to the mixture withcontinued agitation, allowing solvent to fully incorporate. Adddeposition aid polymer followed by water; continue to mix until fullyincorporated. Add preservative, followed by surfactant, then add theprotonating agent and allow the mixture to fully incorporate.

Finish product with continued agitation by adding the dye following thespecified order of addition in Table V below:

TABLE IV Example Aminosilicone-Resin Emulsions Silicone-Resin EmulsionExamples Component (g) AA BB CC DD EE FF Oil Mix. Example 390 39.0 39.039.0 39.0 39.0 U-W Solvent from — 1.5 1.2 0.8 9.75 19.5 examples A-I¹⁻⁹Butyl Carbitol¹¹ 19.5 18.0 18.3 18.7 9.75 0.0 Resin Composition T J, T TT T J-T from Table II Protonating 0.9 0.9 0.9 0.9 0.9 0.9 Agent¹² Water(13.5 g × 3) 40.6 40.6 40.6 40.6 40.6 40.6 Total Amount (g) 100.0 100.0100.0 100.0 100.0 100.0

5. Finished Product Formulation Examples

In a 400 mL beaker, add specified amount of emulsion from examplesAA-FF, followed by perfume; begin mixing solution using an Ika® RWA-20mixer with a 4-blade agitator having 45° pitch on each blade usingappropriate level of agitation. Add solvent to the mixture withcontinued agitation, allowing solvent to fully incorporate. Adddeposition aid polymer followed by water; continue to mix until fullyincorporated. Add preservative, followed by surfactant, then add theprotonating agent and allow the mixture to fully incorporate. Finishproduct with continued agitation by adding the dye following thespecified order of addition in Table V below:

TABLE V Example Finished Product Formulations Finished Product ExampleFormulations Comparative Order of Order of Comparative Order ofComparative Order of Component (g) Example GG Addition HH AdditionExample II Addition Example JJ Addition Emulsion from 25.8 1 25.8 1 25.81 25.8 2 ex. AA-FF Perfume 0.8 2 0.8 2 0.8 2 0.8 3 Butyl 4.0 3 4.0 3 — —4.0 4 Carbitol Solvent ex. — — — 4.0 3 — — A-I Surfactant¹² 0.1 4 0.1 70.1 7 0.1 5 Protonating 0.25 5 0.25 8 0.25 8 0.25 6 Agent¹³ Water 62.656 62.65 5 62.65 5 62.65 1 Deposition 6.35 7 6.35 4 6.35 4 6.35 7 AidPolymer¹⁴ Preservative¹⁵ 0.1 8 0.1 6 0.1 6 0.1 8 Dye¹⁶ 0.004 9 0.004 90.004 9 0.004 9 ¹2-Ethylhexanol: Available from Sigma-Aldrich, St.Louis,MO ²2-Butyloctanol: Available from Sasol Chemical, Johannesburg, SouthAfrica ³2-Hexyldecanol: Available from Sigma-Aldrich, St.Louis, MO⁴Propyleneglycol n-butyl ether: Available from Dow Chemical, Midland MI⁵Dipropyleneglycol n-butyl ether: Available from Dow Chemical, MidlandMI ⁶Tripropyleneglycol n-butyl ether: Available from Dow Chemical,Midland MI ⁷Isopropyl Laurate: Available from Sigma-Aldrich, St.Louis,MO ⁸Isopropyl Myristate: Available from Evonik Corporation, Hopewell,VA. ⁹Isopropyl Palmitate: Available from Evonik Corporation, Hopewell,VA. ¹⁰Silicone MQ Resin: Wacker MQ 803TF, available from Wacker Chemie,AG; Burghausen, Germany ¹¹Butyl Carbitol: available from Dow Chemical,Midland MI ¹²Surfactant: TAE-80, Tallow Alkyl ethoxylate, available fromAkzo-Nobel ¹³Protonating Agent: Glacial Acetic Acid, 97%, available fromSigma-Aldrich, St.Louis, MO ¹⁴Deposition Aid Polymer: Terpolymer ofacrylamide, acrylic acid and methacrylamidopropyl trimethylammoniumchloride; Available from Nalco Chemicals, Naperville, IL ¹⁵Preservative:Proxel GXL, available from Lonza Group, Basel, Switzerland ¹⁶Dye:Liquitint Blue AH; available from Milliken, Spartanburg, SC

Data:

TABLE VI Characterization of Finished product for Appearance andParticle size Finished Product (FP) Formulation Example GG HH II JJCryo-TEM Product Uniform Product Distribution visual Phase particles,Phase of particle appearance split no void split sizes, volumes apparentvoid volumes Avg. Not Tested Not Tested Particle Size (nm.); FP

TABLE VII Stability of Finished Products and Performance FinishedProduct (FP) Formulation Example GG HH II JJ Initial Fail Pass Fail PassProduct Stability Initial TTW Not _% Pass, Not Tested _% Pass,Performance* Tested avg. TTW = avg. TTW = _sec. _sec. 8 Week Not TestedPass Not tested Fail Stability 8 Week TTW _% Pass, _% Pass, _% Pass, _%Pass, Performance avg. TTW = avg. TTW = avg. TTW = avg. TTW = _sec._sec. _sec. _sec.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

1.-11. (canceled)
 12. A method of making a nanoemulsion, comprising thesteps of: a) solubilizing a silicone resin in an organic solvent systemto yield a silicone resin solution concentration of 80% or less, whereinthe organic solvent system comprises diethyleneglycol monobutyl etherand at least one additional solvent selected from the group consistingof monoalcohols, polyalcohols, ethers of monoalcohols, ethers ofpolyalcohols, fatty esters, Guerbet alcohols, isoparaffins, naphthols,glycol ethers or mixtures thereof, provided that if the additionalsolvent is a glycol ether it is not diethyleneglycol monobutyl ether; b)mixing the silicone resin solution from a) with an aminosiloxane polymerto obtain an aminosiloxane polymer:silicone resin mixture having anaminosiloxane polymer to silicone resin weight ratio of 20:1; c)allowing the aminosiloxane polymer:silicone resin mixture to age for atleast 6 hours at ambient temperature; d) adding the aminosiloxanepolymer:silicone resin mixture to a vessel; e) optionally adding withagitation an additional organic solvent to the aminosiloxanepolymer:silicone resin mixture; f) mixing until homogenous; g) adding aprotonating agent; and h) adding an aqueous carrier in an amount toproduce an aqueous nanoemulsion.
 13. The method of making a nanoemulsionof claim 12, wherein the nanoemulsion is substantially free ofsurfactant.
 14. A method of making a nanoemulsion of claim 12, whereinat least one silicone resin is a silicone resin comprising at least 80mol % of units of the formulas 3, 4, 5, and 6:i) R₃SiO_(1/2)   (3),ii) R₂SiO_(2/2)   (4),iii) RSiO_(3/2)   (5),iv) SiO_(4/2)   (6), in which R is H, —OH, or a monovalent hydrocarbonresidue with 1 to 40 carbon atoms optionally substituted with halogens,where at least 20 mol % of the units are units of the formulas 5 and 6,where R¹⁰ is a monovalent hydrocarbon residue with 1 to 10 carbon atoms,and a maximum of 10 wt % of the R residues are —OR and —OH residues. 15.A method of making a nanoemulsion of claim 13, wherein at least onesilicone resin is a silicone resin comprising at least 80 mol % of unitsof the formulas 3, 4, 5, and 6:i) R₃SiO_(1/2)   (3),ii) R₂SiO_(2/2)   (4),iii) RSiO_(3/2)   (5),iv) SiO_(4/2)   (6), in which R is H, —OH, or a monovalent hydrocarbonresidue with 1 to 40 carbon atoms optionally substituted with halogens,where at least 20 mol % of the units are units of the formulas 5 and 6,where R¹⁰ is a monovalent hydrocarbon residue with 1 to 10 carbon atoms,and a maximum of 10 wt % of the R residues are —OR and —OH residues. 16.The method of making a nanoemulsion of claim 12, wherein theaminosiloxane polymer is an aminoalkyl group containingpolyorganosiloxane (P) comprising at least 80 mol % of units of theformulae 7, 8, 9 and 10R¹ ₂SiO_((4-a-b)/2)   (7),R¹ _(a)R² _(b)SiO_((4-a-b)/2)   (8),R³ ₃SiO_((1/2))   (9),R³ ₂R⁴SiO_((1/2))   (10), where a is 0 or 1, b is 1 or 2, a+b is 2, R¹are monovalent hydrocarbyl radicals having 1-40 carbon atoms optionallysubstituted with halogens R² are either a) aminoalkyl radicals of theformula 11—R⁵—NR⁶R⁷   (11) where R⁵ are divalent hydrocarbyl radicals having 1-40carbon atoms, R⁶ are monovalent hydrocarbyl radicals having 1-40 carbonatoms, H, hydroxymethyl or alkanoyl radicals, and R⁷ are radicals of theformula 12—(R⁸—NR⁶)_(x)R⁶   (12) where x is 0 or an integer from 1 to 40, and R⁸are divalent radicals of the formula 13—(CR⁹ ₂—)_(y)   (13) where y is an integer from 1 to 6, and R⁹ are H orhydrocarbyl radicals having 1-40 carbon atoms, or b) in the formula 11R⁶ and R⁷ combine with the nitrogen atom to form a cyclic organicradical having 3 to 8 —CH₂— units, wherein nonadjacent —CH₂— units areoptionally replaced by units selected from —C(═O)—, —NH—, —O— and —S—,R³ are hydrocarbyl radicals having 1-40 carbon atoms optionallysubstituted with halogens, R⁴ are —OR or —OH radicals, and wherein, inthe polyorganosiloxanes (P), the average ratio of the sum of units ofthe formulae 7 and 8 to the sum of units of the formulae 9 and 10 is inthe range from 0.5 to 500, the average ratio of units 9 to 10 being inthe range from 1.86 to 100, and the polyorganosiloxanes (P) have anaverage amine number of at least 0.01 mequiv/g.
 17. The method of makinga nanoemulsion of claim 12, wherein the protonating agent is amonoprotic or multiprotic, water-soluble or water-insoluble, organic orinorganic acid.
 18. The method of making a nanoemulsion of claim 12,wherein the Guerbet alcohol comprises 2-ethylhexanol, 2-butyl octanol,2-hexyl decanol, or mixtures thereof.
 19. The method of making ananoemulsion of claim 12, wherein at least one fatty ester is selectedfrom the group consisting of isopropyl laurate, isopropyl palmitate,isopropyl myristate, isopropyl stearate, isopropyl oleate, isopropyllinoleate and mixtures thereof.
 20. The method of making a nanoemulsionof claim 12, wherein at least one glycol ether is selected from thegroup consisting of mono-, di-, or tri-ethyleneglycol alkyl ethershaving ether moieties containing up to 8 carbon atoms, or mono-, di-, ortri-propyleneglycol alkyl ethers having ether moieties containing up to8 carbon atoms.
 21. The method of making a nanoemulsion of claim 12,wherein the silicone resin is an MQ resin, having a ratio of M units toQ units of 0.5:1 to 1.5:1.
 22. The method of making a nanoemulsion ofclaim 12, wherein the silicone resin is an MQ resin, having a ratio of Munits to Q units of about 0.67:1.
 23. The method of making ananoemulsion of claim 12, wherein at least one protonating agent isselected from the group consisting of formic acid, acetic acid,sulphuric acid, phosphoric acid, hydrochloric acid, citric acid, andmixtures thereof.
 24. A nanoemulsion prepared by the method of claim 12.